Absorption of dye made from

ABSTRACT

ACETOACETAMIDE COUPLERS IN WHICH THE NON-OXO CARBON ATOM OF THE ACETO GROUP IS A TERTIARY CARBON ATOM ARE ADVANTAGEOUSLY USED AS YELLOW DYE-FORMING COUPLERS IN PHOTOGRAPHY; THE COUPLERS ARE CHARACTERIZED BY PRODUCING DYES UPON COLOR DEVELOPMENT THAT HAVE VERY DESIRABLE ABSORPTION CHARACTERISTICS WITH RELATIVELY LOW ABSORPTION IN THE GREEN AND RED AREAS OF THE SPECTRUM, EXCEPTIONALLY GOOD STABILITY TO PROLONGED EXPOSURE TO LIGHT AND THE COUPLERS WHEN INCORPORATED IN PHOTOGRAPHIC EMULSION LAYERS EXHIBIT CONSIDERABLY LESS &#34;PRINT OUT&#34; ON PROLONGED EXPOSURE TO LIGHT AND LESS &#34;YELLOWING&#34; THAN PRIOR ART COUPLERS SUCH AS THE ALPHA-BENZOLYL ANALOGUES.

June 25, 1974 A. WEISSBERGER EI'AL Re. 28,055

ACETOACETAMIDE COUPLERS IN WHICH THE NON-OX CARBON ATOI OF THE ACETO GROUP IS A TERTIARY CARBON ATOM Original Filed May 4:, 1964 I Sheets-Sheet 1.

A ABSORPTION or DYE MADE FROM H3) cco CH2 co NH-Q E Q' u Cl Cz s C5Hu A. As FORMED 1.0 B. AFTER HOURS EXPOSURE IN XEWN ART k c. AFTER nouns FADEOMETER 2 08 m Q 400 20 40 so so 500 20 40 so so 600 20 4o so 700 '4 WAVELENGTH nv MILLIM/CROAS Fig.2 l2 E ABSORPTION 0F DYE MADE FROM (CH3)3 cco CH2 CON/1? 0. A5 FORMED E. AFTERI WEEKINOVEN I40."F,75%RH x h u (1a m Q E 0.6 E -04 0. o

4-00 20 4O 6O 500 20 44D 60 80 600 20 4O 6O 80 700 WAVELENGTH IN MILUMICRONS CHARL ESJ. KIBLER ARNOLD WE ISSBERGER BY INVENTORS M a W 47' DRIVE) 8 AGENT June 25, 1974 A. WEISSBERGER EI'AL Re. 28,

ACETOACETAMIDE COUPLERS IN WHICH THE NON-X0 CARBON ATOI OF THE ACETO GROUP IS A TERTIARY CARBON ATOM Original Filed May 4. 1964 3 Sheets-Sheet 2 v W .1? ir A I2 V F iv 'WW I i ABSORPTION 0F 0 MADE FROM G 05H x ,0 V+ (049 cm CHZCONH @ummko Q 65 (t) n F F. AS FORMED L7) 6. AFTER 3OHOURS EXPOSURE IN FFIDEOMETER m as Q g 0.6 k

0.4 r r r aw A 400 4O 6O 80 500 20 4O 6O 80 600 20 40 6O 80 700 WAVELENGTH IN MILLIMICRONS Fi g. 4 I

r ABSORPTION or DYE MAgE FROM t ,H s um cn cn cu 09C? cOMHQ g H. A5 FORMED I. AFTER HOUR$ EXPOSURE m FAOEOMETER q J I 7* 7', VA .7 A 2 \l k [L 0.4 g 0 Q2 V 400 20 so 500 20 40 so so s00 20 4o 60 so WAVELENGTH m MILLIMICRONS HARLES J. KIBLER ARNOLD WEISSBERGER INVENTORS BY fiMM ATTORNEY a AGENT June 25, 1974 A. WEISSBERGER EI'AL Re. 28,055

ACETOACETAMIDE COUPLERS IN WHICH THE NON-OX0 CARBON ATOI or THE ACE-1'0 GROUP IS A 'rzn'rnmr CARBON ATOM Original Filed May 4, 1964 3 Sheets-Sheet 3 Fig. 5

ABSORPTION OF DYE MADE FROM c H (t (C gbC- mCHZ Qmmcmo J AS FORMED E as If AFTER 30 HOURS EXPOSUREIN 549mm 2 u Q 0.6 i E o 04 WAVELENGTH IN MILLIMICRONS CHARLES -J. K! 8L ER ARNOLD WEISSBERGER INVENTORS' BY flaw/M 3; M W

ATTORNEY G- AGENT United States Patent Oflice Re. 28,055 Reissued June 25, 1974 ACETOACETAMIDE COUPLERS IN WHICH THE NON-OX CARBON ATOM OF THE ACETO GROUP 18 A TERTIARY CARBON ATOM Arnold Weissberger, Rochester, N.Y., and Charles J. Kihler, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N .Y.

Original No. 3,384,657, dated May 21, 1968, Ser. No.

516,802, Sept. 28, 1965, which is a division of application Ser. No. 364,450, May 4, 1964, now Patent No. 3,265,506, which is a continuation-in-part of abandoned application Ser. No. 25,295, Apr. 28, 1960. Application for reissue Aug. 9, 1972, Ser. No. 165,794

Int. Cl. C07c 143/52 US. Cl. 260-507 R 9 Claims Matter enclosed in heavy brackets If] appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE Acetoacetamide couplers in which the non-0x0 carbon atom of the aceto group is a tertiary carbon atom are advantageously used as yellow dye-forming couplers in photography; the couplers are characterized by producing dyes upon color development that have very desirable absorption characteristics with relatively low absorption in the green and red areas of the spectrum, exceptionally good stability to prolonged exposure to light and the couplers when incorporated in photographic emulsion layers exhibit considerably less print out on prolonged exposure to light and less yellowing than prior art couplers such as the alpha-benzoyl analogues.

This is a divisional application of US. patent application Ser. No. 364,450, Yellow-Forming Couplers, filed May 4, 1964 [1962] now US. Patent 3,265,506, issued Aug. 9, 1966. US. Ser. 364,450 is a continuation-in-part application of Weissberger and Kibler US. application Ser. No. 25,295, filed Apr. 28, 1960, now abandoned.

This invention relates to photography and particularly to a new class of yellow dye forming coupler compounds, and their use in photographic elements for color photography.

The formation of colored photographic images in multilayer elements by coupling the oxidation products of aromatic amino developing agents with color forming or coupling compounds is well known. In these processes the subtractive process for color formation is ordinarily used and the image dyes are intended to be of the complementary primary colors, cyan or blue-green, magenta and yelow. The couplers which produce the cyan dyes are usually phenols or naphthols, those producing the magenta dyes are ordinarily pyrazolones and those producing the yellow dyes are ordinarily compounds containing a methylene group having 2 carbonyl groups attached to it. In multilayer elements for color photography the cyan couplers are usually incorporated in the red sensitive layer, the magenta coupler in the green sensitive layer and the yellow coupler in the blue sensitive layer. The dyes produced by coupling are azomethine, indoamines or indophenols depending upon the composition of the coupler and of the developer.

It is important that the dyes formed from couplers used in color photography have the proper light absorption characteristics. Thus, ideally the yellow dye should have a high absorption for blue light and a low but more or less uniform absorption for green and red light. The dyes from many of the available couplers do not possess these absorption characteristics to the desired extent. For example, the yellow dyes from some of the prior art couplers are an orange yellow because they absorbed more green light and less red light than is desired. In order to use such couplers it has been necessary to increase the red light absorption of the resulting dye by mixing a small amount, of the order of 4-l5%, of a cyan dye forming coupler with the yellow dye forming coupler and incorporating this mixture in the blue sensitive layer.

The yellow dyes produced from many of the well known couplers are not as stable as is desired.

Many of the known couplers are unstable themselves and when incorporated in photographic elements are subject to producing discoloration, and effect called printout when caused by exposure to light over a period of time or yellowing, an etfect produced by continued exposure of the coupler to heat. Special processing treatment has been required to reduce the printout and yellowing" effect in photographic emulsions containing some prior art couplers. For example, such residual prior art couplers have been removed from the photographic emulsions after development, bleaching and fixing by treatment with water solutions of various alkalis and a water soluble solvent such as methanol, 1,2-propanediol, 1,3-butanediol, 2,3- butanediol, Z-methoxyethanol, ethanol, ethyleneglycol, npropanol, iso-propanol, Z-methyl-2,4-pentanediol, betabeta'-dihydroxy ethylether, dimethylformamide, propylcneglycol-l,3 ethyleneglycolmonobutylether, diethyleneglycoldiethylether, etc.

It is therefore an object of the present invention to provide a novel class of yellow dye forming couplers which are especially well suited for incorporation in photographic emulsion layers.

Another object is to provide a class of yellow dye forming couplers which produce dyes having unusually good light absorption characteristics.

Another object is to provide a novel class of couplers which has good stability and is not subject to printout" and yellowing" when incorporated in photographic elements.

A further object is to provide a novel class of couplers which produce dyes of exceptional stability.

Other objects will appear from the following description of our invention.

These objects are accomplished according to our invention by the use of a new class of acetoacetanilide type coupler in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom. These couplers can be advantageously represented by the formulas:

wherein Q and Q each represent an acyl group having from 5 to 32 carbon atoms in which the carbon atom attached to the carbonyl radical of said acyl group is a tertiary carbon atom substituted with (a) alkyl radicals having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, tert. butyl, amyl, hexyl, isohexyl, heptyl, octyl nonyl, decyl, dodecyl, tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl etc. (provided not more than 2 of said alkyl radicals are secondary or tertiary alkyl radicals), or (b) alkyl radicals which in turn are substituted with heteroatoms such as halogen, e,g., chlorine, bromine, iodine, etc., or (c) alkoxy radicals such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, dodecoxy, tridecoxy, pentadecoxy, hexadecoxy, heptadecoxy, octadecoxy, etc., or (d) alkoxyalkyl radicals having from 2 to 18 carbon atoms in which the alkoxy moiety and alkyl moiety are as defined above, for example, and can be radicals such as methoxymethyl, methoxyoctyl, methoxyheptadecyl, propoxymethyl, propoxyamyl, propoxypentadecyl, hexadecoxyethyl, etc., or the tertiary carbon atoms attached to the carbonyl radical is substituted as described above but with either 1 or 2 of (a), (b), (c) or (d) radicals above replaced by (e) an aryl radical, e.g., a phenyl radical, a tolyl radical, etc.; or the tertiary carbon attached to the carbonyl radical is an integral component of a cycloalkyl radical such as a l-alkyl-l-cyclohexyl radical in which the alkyl radical has from 1 to 18 carbon atoms as defined above, such as l-methyl-l-cyclohexyl, l-ethyl-l-cyclohexyl, l-propyl-l-cyclohexyl, l-hexyl-l-cyclohexyl, 1-octadecyl-lcyclohexyl, etc., a l-alkoxyl-cyclohexyl radical in which the alkoxy radical contains from 1 to 18 carbon atoms as defined above, such as 1 methoxy 1 cyclohexyl, 1 ethoxy 1 cyclohexyl, 1 propoxy 1 cyclohexyl, 1 nonoxy 1 cyclohexyl, 1 octadecoxy 1 cyclohexyl, a l alkoxyalkyl 1 cyclohexyl radical in which the alkoxyalkyl radical has from 2 to 18 carbon atoms as defined above, such as l-methoxymethyl-l-cyclohexyl, 1 methoxybutyl-l-cyclohexyl, l-hexadecoxymethyl-l-cyclohexyl, etc., a l-aryl-l-cyclohexyl radical such as l-phenyl-lcyclohexyl, 1 tolyl-1- cyclohexyl, etc., a ring-substituted l-alkyl-l cyclohexyl radical, a substituted l-alkoxy-l-cyclohexyl radical, a substituted 1-alkoxyalkyl-l-cyclohexyl radical as defined above in which the substituent is an aryl radical such as phenyl, tolyl, etc., an alkyl radical having from 1 to 12. carbon atoms including those defined above, an alkoxy radical having from 1 to 12 carbon atoms including those defined above, such that the acyl groups Q and Q each have a total of from 8 to 31 carbon atoms; or the tertiary carbon atom attached to the carbonyl radical is an integral component of a bicyclic radical, e.g., a terpenyl radical, such as 7,7-dimethylnorbornyl, 2-alkyl- 7,7-dimethylnorbornyl radicals in which the alkyl group has from 1 to 18 carbon atoms as defined above, such as 2-methyl-7,7-dimethylnorbornyl, 2-pentadecyl-7,7-dimethylnorbomyl, 2-octadecyl 7,7 dimethylnorbornyl, etc., a 2-aryl-7,7-dimethylnorbornyl radical such as 2-phenyl- 7,7-dimethylnorbornyl, 2-tolyl-7,7-dimethylnorbornyl, etc., A and A each represents a hydrogen atom, a halogen atom such as chlorine, or bromine, or a -SB radical in which E is a heteocyclic radical such as 1,3,4-oxadiazolyl, benzoxazole, phenyltetrazolyl, etc., a substituted phenyl radical such as a 3-alkylcarbamylphenyl in which the alkyl group has from 1 to 18 carbon atoms, such as 3-methylcarbamylphenyl, 3 ethylcarbamylphenyl, 3-propylcarbamylphenyl, 3 hexylcarbamylphenyl, 3-decylcarbamylphenyl, 3-tetradecylcarbamylphenyl, 3-octadecylcarbamylphenyl, etc., a 3-alkyl-4-methoxyphenyl radical, in which the alkyl group has from 1 to 18 carbon atoms such as 3-methyl-4-methoxyphenyl, 3-propyl-4-methoxyphenyl, 3-nonyl-4-methoxyphenyl, 3-octadecyl-4-methoxyphenyl, etc., a dialkyl-4-arninophenyl radical in which the alkyl groups have from 1 to 18 carbon atoms such as 2,6-dimethyl-4-aminophenyl, 2,6-diethyl-4-aminoph yl, 2,6-dipropyl-4-aminophenyl, 2,6-dioctyl-4-aminophenyl, 2,6-ditetradecyl-4-aminophenyl, 2,6 dioctadecyl-4-amino- Phgnylr yl 4 aminophenyl, 3,5dipropyl-4 aminophenyl, 3,5-didodecyl 4 aminophenyl, octadecyl, etc.; and R and R each represent the same or a different group, e.g., an aryl group such as phenyl, Z-chlorophenyl, 4-sulfopheny1, Z-dimethylaminophenyl, etc., a Z-halo-S- alkamidophenyl radical, e.g., Z-chloro-S-[alpha-(2,4-ditert amylphenoxy)acetamido]phenyl, Z-chloro-S-[alpha- (2,4-di-tert-amylphenoxy)butyramido]phenyl, 2-chl0ro-5- [alpha-(2,4 di tert amylphenoxy)arnylamido1phenyl, 2-chloro-5-[w-(2A di tert amylphenoxy)butyramido] phenyl, 2-chloro-S-(4-methylphenyl sulfonamido)phenyl, 2fluoro'5-(N hexylamido)phenyl, etc., a Z-methoxy-S- alkamidophenyl radical, e.g., Z-methoxy 5 (2,4-di-tertamylphenoxy)acetamidophenyl, 2 methoxy-S-[alpha-(Z. 4-di-telt-amylphenoxy)butyramidolphenyl, etc., a 4-alkamidophenyl radical, e.g., 4-(2,4 di tert-amylphenoxy) acetamidophenyl, 4-[7 (2,4-di-tert-amylphenoxy)butyramido]phenyl, etc., a 4 -methoxyphenyl radical, e.g., 4- [N-(' -phenylpropyl) N (p tolyl)carbamylmethoxy1 phenyl, 4 [N ('y phenylhexyl)-N-(p-tolyl)carbamylmethoxy]phenyl, etc., a 4-sulfamylphenyl radical, e.g., 4-[N-(v phenylpropyl)-N-(p-tolyl)sulfamyl]phenyl, 4- [N-(phenylethyl)-N-(p-tolyl)sulfamyl]phenyl, etc., a 2- chloro-S-sulfonamidophenyl radical, e.g., 2 chloro-S-(ptoluenesulfonamido)phenyl, 2 chloro-S-(benzenesulfonamido)phenyl, etc., a 3,5-dicarboxypheny1 radical, esters of 3,5-dicarboxyphenyl radicals, e.g., 3,5-dicarbomethoxyphenyl 3,4 dicarbohexoxyphenyl, 3,5-dicarbododecoxyphenyl, 3,5 dicarbopentodecoxyphenyl, 3,5-dicarbooctadecoxyphenyl, etc., a Z-phenoxy-5-carbamylphenyl radical, e.g., 2-(2,4-di-tert-amylphenoxy) 5 (3,5-dicarbomethoxyphenylcarbamyl)phenyl, 2 (2,4-di-tert-amylphenoxy) 5 (N-morpholinocarbonyl)phenyl, etc., a 3,5-di carbamylphenyl radical, etc.; the hydrogen atom; an alkyl group of 1-18 carbon atoms, e.g., methyl, ethyl, decyl, octadccyl, carboxymethyl, carboxyoctadecyl, carbomethoxymethyl, carbobutoxypropyl, beta hydroxyethyl, w-chloropropyl, 'y acetamidopropyl, 'y-methylcarbamylbutyl, beta-methylsulfonamidoethyl; and a heterocyclic radical selected from those of the thiophene series, e.g., a S-carbethoxythiophenyl-(2)-radical, those of the furane series, e.g., a S-carbethoxy-furyl radical, those of the thiazole series, e.g., a 4-methyl-thiazlolyl-(2)-, a 4 -phenylthiazolyl-(2)-, a 4 furyl thiazolyl-(2)-, a 4-methyl-5- carboxyethyl-thiazolyl-(2)-, a 4,5-diphenylthiazolyl-(2)-, a 4-carboxymethyl-thiazolyl-(2)-, a 4-mor p-acylaminophenyl-thiazoly1-(2)-, a 4,5-dicarbethoxy-thiazolyl-(2)-, a 4 methyl-5-carbethoxymethyl-thiazolyl-(2)-, a 4-methyl- S-carbethoxythiazolyl-(Z)-, a 5-carboxy-thiazolyl-(2)-, a Scarbomethoxy-thiamlyl-(2)-, a S-carbethoxy-thiazolyl- (2)-, a S-carbethoxy-thiazolyl-(2)-, or a benzthiazolyl- (2)-radical, those of the oxazole series, those of the imidazole series, e.g., a benzimidazyl-(Z)-radical, those of the pyridine series, e.g., a S-acylamino-pyridyl-(2)-, a pyridyl-(4)-, or a quinolyl-(2)-radical, those of the 1,3- or 1,4-diazine series, e.g., a 2,6-dihydroxy-4-methyl pyrimidyl-(5)-radical, those of the 1,3,4thiadiazole series, e.g., a S-carbomethoxyethyl-1,3,4-thiadiazolyl-(2)-radical, those of the 1,3,4-oxodiazole series, those of the 1,2,4- tr azole series e.g., a 1- (p carbethoxyphenyl)-3-aminotriazolyl-(5)- or a 1 (o carbethoxyphenyl)-3-aminotriazolyl-(5)- or a l (p carbethoxyphenyl)trioxolyl-(5)- radical and those of the 1,3,5-triazine series; D and D' Gail; represent the same or a different bivalent group such as e group, the

group, the NHSA2' group, the -SO NH group, etc.; and W represents a phenylene group, e.g., an o-phenylene, a p-phenylene or an m-phenylene group or an alkylene group having from 1-18 carbon atoms, e.g., methylene, butylene, decylene, octadecylene, etc.

By tertiary carbon atoms we mean a carbon atom which is in turn connected to 3 other carbon atoms either directly or through an oxygen atom (as in alkoxy) which in which X, Y and Z each represent (a) an alkyl radical having from 1-18 caron atoms, e.g., methyl, ethyl, isopropyl, butyl, tertiary butyl, isohexyl, isooctyl, octadecyl, etc., provided that not more than two of the said alkyl are a part of individual radicals, or a carbon atom which radlcals IS a Secondary or tfimary alkyl Tadlcalall is 111 turn connected to three o r a n at s w i h alkyl radical as defined above substituted with hetero are members of cyclic or blcychc q atoms, e.g., halogen, (c) an alkoxy radical having from Our couplers WhlCh have only Individual radicals at- 1 t 18 b t th b t h tached to the tertiary carbon atoms can also be repre- 10 0 car on a 01m, me u my, cxoxy, sented by h for ul dodecoxy, pentadecoxy, octadecoxy, etc., (d) an alkoxy- X 0 0 R alkyl radical having from 1 to 18 carbon atoms in which L P; P the alkoxy and alkyl radicals are as defined above, the i A total number of carbon atoms in X plus Y plus Z is no and more than 30 in any of the radlcals described above, and HA x 0 0 R A, R, R, D, D and W are as previously described.

J, E P, ,L The following are representative couplers used to illusi D trate our invention and are not to be considered as limit- L, ing the invention. X 0 R 1 g I Y- CHC- Coupler number Name 1 Alpha-pivalylacetanillde.

0 4% ll (CHmC CHJJNHCJI.

2. Alpha-plvaly1-2-chl0r0a/rotanillde. 3. Alpha-pivaly 2-(2 dlmethylaminlnoJacetnnlllde. 4- Alpha-pivalyl-5-lalpha'-(2,4-di-tert-amylphenoxy)11cctamidol-2-chlornacetanHide.

01 0 O 2} ll (CHmC 011mm! 0 05mm) NHCCII3O b il( 5 Alpha-pivalyl-alpha-chloro-fi-[alphn'-(2,4-di-tert-amylphcnoxy)acetamido]-2- chloroacetauilide. A1pha-(alpha-rnetl1oxyisobutyryl)-5[alpha' '-(2,4-di-tert-amylphenoxymcetamldo] 2-chloroacetanilide. Alpha-(ririehoxyplvalyl)-5-[alpita-(2,4-di-tert-umy1phenoxy)acuiamldolJ-chloro acetan i e. Alpha-pivalyl-5-{alpha-(2,4-di-tert-amylphenoxy)-acetamido]-2-methoxyace1an-ilide.

Alpha-pivalyl-5-[alpha (2,4-di-tert-arnylphenoxy) -butyramido1-2-chloroacetanllidr.

Alphapivaly]-5-[-r -(2,4-di-tert-amylphenoxyj-butyramido]-2-chloroaoetauilide.

Alpha-(chloropivalyl)-5-[v'-(2,4 dl-tert-amy1phenoxy)-butyramid0]-2-chloroacetanilide.

Alpha-(alpha-methoxylsobutyry])-5-l'y"-(2,4-di-tert-arnylpheuoxy)butyramido1-2- chloroacatanllide.

Al ha-pivalyl-alpha[2-(5-pheny1-1,3,4oxadlaZ0lyl-tl1io)]-5-[ -(2,4-di-tert-amy lphenoxy)2- utyramido-12-chloroacetunilide.

Cl 0 0 ll A Q-5 HN CrH (U S H (I) NIIC-(CH2)r-O C li 1lt) N- l O N-('J 14 Alpha-pivalyld [N-(-y-pherlylpropyn-N-(p-tO]yl)-t'arbamylmetlloxyllncetanilidn. 15 Alpha-pivalyl-4 [N-(y-phenylpropyD-N-(p-tolyl)'sulfamyflacetanillde.

(CHzhClHg 16 Alpha-pivalyl-5-(p-toluenesultonamido)-2-chloroacntanilide.

Alpha-pivaly]-2-(ZA-dt-tert-amylphenoxy)-5-N-(morpholinocarbonybacetanillde. Alpha-pivalyl-alpha-(El-octadecylcarbamyiphenylthio) -3,5-di-ca.rbomethoxyacetauilide. Alpha-pivalyl-Bflioarboxyacetaniiide. Alpha-pivalyi-alpha-(3-tetradecylcarbamylphenylthio)-3,5-dicarboxyacetanilide. Alpha-pivaly1-3,5-dicarbododeoyloxyacetanilide. Alpha-pivalyl-3,5-dicarbnmylacetanilide. Alpha-pivalyl-3,5-dl-(N-ootlcarbamyhacetanilide.

Alpha-pivalyl-4 sulfoucetan 1 ide potassium salt.

25 A]pl;a-pivalyl-alpha-(3outadecy1carhamylphenylthin)-4-sulfoacetanilida potassium sa t. 26 Alpha-(alpha,alpl1a-dimethylstearoyl).4.sultoacntanilidn potassium salt.

TABLE-Continued Coupler number Name 27 Alpha- (alpha',alpha',di-n-amyl) heptanoyl-S-heptanamldo-2-fiuoroaeetanllide. 2B Alpha-(7,T-dimethylnorbornane-l-carbonyl)alpha (3 octadecylcarbamylphenylthio) 3,5 dlcarboxyacetanilide.

CHz-CH2 COOH'.

i l i i II C -CC-(|J HU NH- C H; S CH -Gllg COOH O i! UN H 0131131 29 Alpha-(7,7-dlmell1ylnorbornane-I-carbonyl)-5-['y-(2,4-di-tert-amylphenoxy)butyrarnidol- Z-chloroacetanilide. 3D Alpha-(l-methyleyclohexane-l-earbonyll-S-[y-(2,4-di-tert-amylphenoxy)butyramido] 2-chluroacetanilide.

3! Alpha-pivay1-2,5-dichl0ro-4-(N-methyl-N-octadecylsulfamyl)acetanilide.

Alpha-plvalyl-2-chloro-4-(N-lnethyl-N-octadocyl-sulfamyl)acetanilide.

Alpha-pivalyl-2-chloro-4-(N-phenyl-N-octadecyl-sulfa1nyl)acetanilide.

Alpha'pivalyl-2-chloro-4-lN-benzyl-N-(I-methyldodecyl)-sultamyl]a.cetanilide. Alpha-pivalyl-2,5-dichloro-4-(N-phenyl-N-0ctadecyl-sulfamyl)acetanillde.

Alpliwpivalyl-2,5-dlchloro-4-lN benzyl-N-l-m et hyldodecylJsulfamyHacetanilide.

3T Alpha-(alphmalpha-diphenylbutyryD-fi-[T-(2, i-di-tert-amylphenoxy)butyramido1- 2-ehlor0aeetanilide.

3S Alpha-(alpha-phenylisobutyryl)-5-[-y-(2,4-di-tert-amylphenxoy)butyraniidol- Z-ehloroacetanilide.

39 Alpha-(alpha. phenylisobutyryl)-alpha-t3-octadecyl carbamylphenylthio)-4- sultonacetanilide potassium salt monohydrate.

icarboxymcetamhde.

. Alpha-plvalyl-N-(2 thiazolyDacetamlde.

. Alpha-pivalyl-N ,N bis(carbethox3mtethyl)acetamide.

-. Al ha-(alpha-pheuyllsobutyryl)-alpha (3-00tadecyl-carbamylphenylthio)-3,5-

43: Alpha-pivalyl-alpha-octadecylthlo3,5-dicarboxy-acetanilide.

4-1 Alpha-rrixigalyl-alpha-(is octadecylcarbainylphenylthi0)-N ,N-bis(carboxymethyl) aceta (e.

45 Alpita-plvalyl-N-(4,5-dicarbethoxy-Z-thiazolyl)acetamide.

46 N ,N'-bis[4-(alpha-ptvalylacetamide)-benzenesulI0nyll-hexamethylenediamlne.

| crime omli NHS ogtfrr The compounds of our invention are prepared to advantage by the reaction of the appropriate acylacetic ester having the formula:

group, with an appropriate amine having the formula:

IV R

in which R and R are as defined previously to give a compound of the formula V OR These reactions are usually carried out in a suitable solvent, such as, xylene, while the mixture is stirred and refluxed. Compounds of Formulas I and II in which A is other than the hydrogen atom are prepared by treating the appropriate compound of Formula V with an appropriate reagent, e.g., an aryl sulfenyl halide prepared by the reaction of an aryl disulfide or aryl mercaptan with a halogen; or a heterocyclic sulfenyl halide prepared by reaction of a heterocyclic disulfide or a heterocyclic mercaptan with a halogen, sulfuryl chloride, etc.; an alkyl disulfide or alkyl mercaptan with a halogen, sulfuryl chloride, etc.

Compounds of Formula IA are prepared to advantage by reacting (1) a compound of Formula I in which R represents an aminophenyl group, a chlorosulfonylphenyl group or a chlorocarbonylphenyl group with (2) a compound having the formula:

in which L and L' each represents a group, such as the group, the SO Cl group or the NH, group and the condensation of two moles of the compound of Formula. I with one mole of LWL' forms one molecule of the new coupler and two molecules of HCl. The reaction is conducted in an inert dry solvent such as dry dioxane and in the presence of a tertiary amine such as triethylamine as an acid acceptor.

Coupler 1 was prepared by the reaction of equimolar quantities of ethyl pi'valylacetate and aniline in refluxing xylene (600 mL/mole of reactants). After a reaction period of 1 hour, the solution was cooled; the product was obtained as coarse white crystals having a M.P. of 77-79" C.

Coupler 2 was prepared from ethyl pivalylacetate and 2-ch1oroaniline by the procedure described for coupler 1, and was obtained as a solid with a M.P. of 48-50 C.

Coupler 3, prepared from ethyl pivalylacetate and 2- dimethylaminoaniline by the procedure described for coupler 1, was obtained as a solid with a M.P. of 68- 70 C.

Coupler 4 was prepared by using the following steps:

Step 1.--a-(2,4-di-tert-amylphenoxy)-4-chloro-3-nitroacetanilide To a stirred mixture of 677 g. of anhydrous sodium acetate, 8 liters of glacial acetic acid, and 448 g. of 4- chloro-S-nitroaniline was added 847 g. of (2,4-di-tertamylphenoxy)-acetyl chloride. The resulting suspension was stirred for 5 hours at room temperature, then poured into 20 liters of water. The solid obtained was recrystallized from alcohol to give 830 g. of white flakes, M.P. 157-158 C.

9 Step 2.[a-(2,4-di-tert-amylphenoxy)-acetamido]- 2-chloroaniline A solution of 44.6 g. of a-(2,4-di-tert-amylphenoxy- 4-chloro-3-nitroacetanilide in 200 ml. of absolute ethanol was placed in a Parr shaker bottle and hydrogenated at room temperature in the presence of Raney nickel catalyst. The initial pressure of hydrogen was 50 p.s.i., and the reduction was complete in 1 to 1 hours. The mixture was heated to boiling and filtered, and the filtrate was added to 1500 ml. of water. There was thus obtained 32 g. of product, M.P. 117-l18 C.

Step 3.a-Pivalyl-5-[01-(2,4-di-tert-amylphenoxy)- acetamido] -2-chloroacetanil ide To a refluxing solution of 318 g. of 5-[a-(2,4-di-tertamylphenoxy)-acetamide1-2-chloroaniline in 2 liters of xylene was added 125 g. of ethyl pivalylacetate. The mixture was boiled for 2 hours, during which time ethanol and some xylene were removed by distillation. The mixture was then filtered into 4 liters of ligroin and cooled; the product thus obtained was recrystallized twice from alcohol to give coupler 4, M.P. 139-140 C.

Coupler 5.--A stirred solution of 25 g. of coupler 4 in 150 ml. of chloroform was cooled in an ice bath, and a solution of 6.48 g. of sulfuryl chloride in 25 ml. of chloroform was added over a period of /2 hour. The mixture was stirred at room temperature for 4 hour, and the solvent was then removed under vacuum. The residue was recrystallized twice from hexane to give 21.3 g. of coupler 5, M.P. ll03 C.

Coupler 6 was prepared by the reaction of 4.18 g. of methyl a-(a'-methoxyisobutyryl)-acetate and 10.0 g. of 5 [or (2,4 di tert amylphenoxy) acetamido] 2- chloroaniline in 75 ml. of xylene, according to the procedure used for coupler 4 in Step 3. There was thus obtained 9.0 g. of product, which was recrystallized twice from a mixture of hexane and ethanol to give 5.79 g. of coupler 6, M.P. 106-109 C.

Coupler 7 was prepared by the reaction of 7.67 g. of 5 [a (2,4 di tert -amylphenoxy) acetamide] 2- chloroaniline and 3.46 g. of methyl a-(methoxypivalyU- acetate in 50 ml. of xylene, in a manner similar to that described for coupler 4, Step 3. There was thus obtained, after one recrystallization from a mixture of hexane and ethanol, 7.72 g. of a white crystalline product, M.P. IDS-110 C.

Coupler 8, prepared by the reaction of ethyl pivalylacetate with 5-[u-(2,4-di-tert-amylphenoxy)-acetamido] 2-chloroaniline according to a procedure similar to that used for coupler 4 in Step 3, was obtained as a white solid with a M.P. of 106108 C.

Coupler 9 was prepared from ethyl pivalylacetate and 5 [a' (2,4 di tert amylphenoxy) butyrarnido] 2- chloroaniline by a method similar to that described for coupler 4 in Step 3. The product was recrystallized from alcohol to give a White solid, M.P. 985-400 C.

Coupler 10 was prepared by the following steps:

Step 1. y-(2,4-di-tert-amylphenoxy)-4-chloro-3- nitrobutyranilide To a stirred mixture of 107.5 g. of anhydrous sodium acetate, 96.0 g. of 4-chloro3-nitroaniline, and 1500 ml. of glacial acetic acid was added 180 g. of 'y-(2,4di-tertamylphenoxy)-butyryl chloride. The resulting mixture was stirred at room temperature for hour, permitted to stand overnight, and poured into 4500 ml. of water. The gummy product was separated, washed with water, and recrystallized twice from methanol to give yellow crystals, M.P. 86-91" C.

Step 2.5-['y-(2,4-di-tert-amylphenoxy)-butyramido]- 2-chloroaniline The reduction of -(2,4-di-tert-amylphenoxy)-4-chloro- 3-nitrobutyranilide to 5 ['y (2,4di-tert-amylphenoxy)- Cit bntyrarnido]-2-chloroaniline was accomplished in a manner similar to that described for coupler 4 in Step 2. From the hydrogenation of 47.5 g. of the starting nitro compound there was obtained, after two recrystallizations from cyclohexane, 36 g. of product, M.P. 113-1l5 C.

Step 3.--a-pivalyl-5- [y-(2,4-dl-tert-amylphenoxy)- butyramido]-2-chloroacetanilide The reaction of 5-[y-(2,4-di-tert-amylphenoxy)-butyramido]-2-chloroaniline and ethyl pivalylacetate in xylene solution was carried out by a procedure similar to that described for coupler 4 in Step 3. The product was recrystallized from methanol to give coupler 10 as a white solid, M.P. 55-60 C.

Coupler 11 was prepared from 13.35 g. of 5-[ -(2,4- di-tertamylphenoxy) butyramidol-2-chloroaniline and 5.78 g. of methyl ot-(chloropivalyl)-acetate in 225 ml. of xylene by a procedure similar to that described for coupler 4 in Step 3. The crude product was recrystallized three times from hexane to give coupler ll, M.P. 99 C.

Coupler 12.The reaction of methyl a-(amethoxyisobutyryl)-acetate with -5 ['y-(2,4-di-tert-amylphenoxy)- butyramido]2-chloroaniline in xylene solution was carried out in a manner similar to that described for coupler 4 in Step 3. The crude product was recrystallized from a mixture of hexane and ethanol to give the coupler 12 as awhite solid, M.P. 8889 C.

Coupler l3.Chlorine gas was passed through a susension of 8.9 g. of 2-mercapto-5-phenyl-l,3,4-oxadiazole in 75 ml. of carbon tetrachloride until complete solution was attained. The solution was evaporated to dryness under vacuum and at room temperature, and the residue was dissolved in 700 ml. of toluene. To this solution was added 22.5 g. of coupler 10, and the mixture was heated at 75 C. for 4 hours, then concentrated under vacuum and at room temperature. The oily residue was extracted with methanol, and the extracts were concentrated to a residue which was then dissolved in acetic acid. Upon dilution of this solution with a large volume of water, the coupler was obtained as a gray-white solid, M.P. 112 C.

Coupler 14, prepared from equimolar quantities of ethyl pivalylacetate and 4-[N-('y-phenylpropyU-N-(p-tolyl)-carbamyl-methoxy]-aniline in a manner similar to that described for coupler 1, was obtained as a solid having a M.P. of 118l20 C.

Coupler 15, prepared from ethyl pivalylacetate and 4- [N-( -phenylpropyl) N (p-tolyl)-sulfamyl]-aniline by method similar to that used to prepare coupler l, was obtained as a solid with a M.P. of l58159 C.

Coupler 16.--The reaction of ethyl pivalylacetate with S-p toluene-sulfonamido-Q-chloroaniline in boiling xylene by a procedure similar to that described for coupler 4 in Step 3 yielded a product which was recrystallized from alcohol to give the coupler M.P. 192.5 C.

Coupler l7.-The reaction of 2.0 g. of 2-(2',4'-di-tertamylphenoxy) 5 (N-morpholinocarbonyl)-aniline and 1.7 g. of ethyl pivalylacetate in 15 ml. of xylene was carried out in a manner similar to that used for coupler l. The product was recrystallized from methanol to give 1.5 g. of the coupler as white crystals, M.P. 178-180" C.

Coupler 18 was prepared by using the following steps:

Step l.a-pivalyl-3,5dicarbomethoxyacetanilide A mixture of 40 g. of 3,5-dicarbomethoxyaniline, 64 g. of ethyl pivalylacetate, 1 g. of anhydrous sodium acetate, and one liter of xylene was refluxed for 2 hours. The ethanol which formed was removed by distillation. The mixture was diluted with ligroin, concentrated by distillation, and cooled to yield .50 g. of product. Recrystallization of the product from a mixture of methanol and water yielded material having a M.P. of ll0l 12 C.

1 1 Step 2 To a saturated solution of chlorine in 250 ml. of carbon tetrachloride at a temperature of -5 C. was added 16.2 g. of bis-(3-octadecylcarbamylphenyl)-disulfide. The mixture was stirred at 25-35 for 1 /2 hours, then concentrated under vacuum to a yellow residue. This residue was dissolved in 400 ml. of carbon tetrachloride, and to the solution was added a slurry of 13.4 g. of a-pivalyl- 3,S-dicarbomethoxyacetanilide in 100 ml. of carbon tetrachloride. The mixture was heated under reflux for 2 /2 hours, then cooled to room temperature. The crude product which separated was collected and recrystallized twice from carbon tetrachloride to give 16.8 g. of coupler 18, M.P. 120-121 C.

Coupler l9.--A slurry of 17 g. of a-pivalyl-3,5-dicarbomethoxyacetanilide in 200 ml. of alcohol was added to a solution of 7 g. of sodium hydroxide in 100 ml. of water. The mixture was heated at a temperature of 55- 60 C. for 1 hour, then poured into 60 ml. of glacial acetic acid. The crude product obtained on cooling was separated and extracted with a mixture of alcohol and ether. The solid obtained by concentration of the extracts was dissolved in alcohol, and this solution was poured into a mixture of ice and acetic acid. The coupler was obtained as a white solid, M.P. 271.5-272.5 C. (dec.).

Coupler 20 was obtained by using the following steps:

Step L-a-Piv alyl-a- 3-tetradecylcarbamylphenylthio) -3 ,5 -di-carbomethoxyacetanilide This compound was prepared from 11.0 g. of bis-(3- tetradecylcarbamylphenyl)-disulfide and 10.0 g. of a-pivalyl-3,S-dicarbomethoxyacetanilide by a method similar to that employed in the preparation of coupler 18. The crude product obtained was recrystallized from carbon tetrachloride to give 8.5 g. of a white solid, M.P. 134- 135 C.

Step 2.a-Pivalyl-a- 3-tetradecylcarbamylphenylthio)-3,S-di-carboxyacetanilide A suspension of 4.25 g. of a-pivalyl-a-(3-tetradecylcarbamylphenylthio)-3,S-dicarbomethoxyacetanilide in 40 ml. of ethanol was treated with 4 ml. of 40% aqueous sodium hydroxide was stirred and heated on a steam bath for 15 minutes. Upon cooling, the mixture was diluted with ethanol and water, then filtered into diluted hydrochloric acid. There was obtained 3.5 g. of coupler M.P. l70-l73 C.

Coupler 21.-The reaction of 6.27 g. of di-carbododecyloxyaniline and 2.06 g. of methyl pivalylacetate in 45 ml. of xylene in a manner similar to that described for coupler 4 Step 3, yielded a waxy solid, which was recrystallized several times from isopropyl alcohol to give 4.30 g. of coupler, M.P. 60-64" C.

Coupler 22 was prepared by using the following steps:

Step 1.3,5-di-carbamylnitrobenzene A mixture of 50 g. of S-nitroisophthalic acid and 250 ml. of thionyl chloride was heated under reflux overnight. The mixture was concentrated under vacuum to a solid residue, which was extracted with anhydrous ether. The ethereal extract was added dropwisc, with stirring, to a solution of anhydrous ammonia in 250 ml. of ether. The product separated from solution and was collected and dried; 28 g. of a colorless solid was obtained.

Step 2.3,5-di-carbamylaniline A solution of 20 g. of 3,5-di-carbamylnitrobenzene in absolute ethanol was hydrogenated at room temperature and an initial hydrogen pressure of 50 p.s.i. in the presence of palladium on charcoal catalyst. The catalyst was removed by filtration, and the filtrate was evaporated to yield 15.8 g. of a tan solid, MJP. 250-253 C. (dec).

1 2 Step 3.a-Pivalyl-3,5-dicarbamylacetanilide A solution of 8.0 g. of methyl pivalylacetate was added to a solution of 8.8 g. of 3,5-di-carbamylaniline in 500 ml. of xylene containing 0.5 g. of anhydrous sodium acetate. The resulting mixture was refluxed overnight; 10 ml. of distillate was collected during this time. Upon cooling, the coupler was obtained as a colorless solid, M.P. 241-243 C. (dec.).

Coupler 23.3,5-di-(N-octylcarbamyl)-aniline was prepared by hydrogenation of the product of reaction between Smitroisophthaloyl chloride and n-octylamine; the procedure employed was similar to that used for coupler 22 in Steps 1 and 2. Reaction of ethyl pivalylacetate with 3,S-di-(N-octylcarbamyl)-aniline in xylene solution in a manner similar to that described for coupler 22 in Step 3, yielded coupler 23, M.P. 88-90" C.

Coupler 24 was obtained by using the following steps:

Step l.Alpha-pivalyl-4-chlorosulfonylacetanilide To 350 ml. of chlorosulfonic acid 44 g. of coupler l was slowly added; the temperature was maintained below 8 by cooling. The mixture was stirred, with cooling, for 2 hours after addition was complete. After standing overnight the mixture was poured on ice, and the product which separated was extracted with ethyl acetate. The

extracts were washed with water, dried and concentrated to dryness under vacuum to yield 31 g. of a pale yellow solid.

Step 2.Alpha-pivalyl-4-sulfoacetanilide potassium salt A solution of one part alpha-pivalyl-4-chlorosulfonyl in 10 parts of methanol was refluxed for 3 /2 hours, then filtered and concentrated under vacuum to dryness. The residue was dissolved in water and treated with a saturated aqueous solution of potassium acetate. The solid which separated was recrystallized to give coupler 24 as a White solid which decomposed without melting at 270 C.

Coupler 25.Alpha pivalyl-alpha-(3-octadecylcarbarnylphenylthio)-4-chlorosulfonylacetanilide was prepared, according to a procedure similar to that described for coupler 18, from 40 g. of bis(3-octadecylcarbamylphenyl)- disulfide and 31 g. of alpha-pivalyl-4-chlorosulfonylacetanilide (prepared as indicated for coupler 24 in Step 1). The crude product was dissolved in 700 ml. of methanol, and the mixture was refluxed for 3 /2 hours, then filtered, concentrated to one-half its original volume, and treated with 10 g. of potassium acetate. The solid material which separated was recrystallized from methanol to give coupler 25 as a white solid.

Coupler 26 may be prepared by the following steps:

Step l.-Alpha-(alpha',alpha'-dimethylstearoyl) acetanilide Reaction of methyl alpha-(alpha,alpha'-dimethylstearoyl)acetate with aniline in a manner similar to that used to prepare coupler 1 would yield alpha-(alpha',alpha'- dimethylstearoyl acetanilide.

Step 2.--Alpha-(a1pha,alpha-dimethylstearoyl)- 4-chlorosulfonylacetanilide Treatment of alpha-(alpha',alpha'-dimethylstearoyl)- acetanilide according to a procedure similar to that described for coupler 24 in Step 1, would yield alpha-(alpha', alpha-dimethylstearoyl)-4-chlorosulfonylacetanilide.

Step 3.-Alpha (alpha',alpha'-dimethylstearoyl)-4- sulfoacetanilide potassium salt Treatment of the chlorosulfonated coupler prepared in Step 2 with methanol and potassium acetate in a manner similar to that described for coupler 25 would yield coupler 26.

Coupler 27 may be prepared from methyl alpha-(alpha',alpha' di n amyl)heptanoylacctate and S-heptanamido-2-fluoraniline by a procedure similar to that described for coupler 4 in Step 3.

Coupler 28 was prepared by the followings steps:

Step l.Ethyl-7,7-dimethynorbornane-l-carboxylate A mixture of g. of 7,7-dimethylnorbornane-l-carboxylic acid (prepared by the method of D. N. Kursanov and S. V. Vitt, Zhur, Obschei Khim, 25, 2509 (1955) and ml. of thionyl chloride was refluxed for minutes. After removal of excess thionyl chloride by distillation under vacuum, a solution of 10 ml. of absolute ethanol in 50 ml. of dry ether was added. The resulting mixture was refluxed for 15 minutes, then cooled, washed with water, dried over magnesium sulfate, and distilled to give 11 g. of a colorless liquid, B.=P. 103 104 C. (18 mm.).

Step 2.-7,7-dimethyl-1-cyanoacetylnorbornane A solution of 4.1 g. of acetonitrile in 15 ml. of ether was added to a suspension of sodamide (prepared from 2.3 g. of sodium metal) in 200 ml. of liquid ammonia. After 5 minutes of solution of 9.8 g. of ethyl 7,7-dirnethylnorbornane-l-carboxylate in 15 ml. of ether was added, and, after 30 minutes, 200 ml. of ether was added. The mixture was warmed to drive off excess ammonia, then poured into 500 ml. of water. The aqueous phase was separated, acidified with acetic acid, and extracted with ether. The extracts were concentrated, and the residue was recrystallized from a mixture of ether and petroleum ether to give a white solid, M.P. 5860 C.

Step 3.-Methyl alpha-(7,7-dimethylnorbornane-1- carbonyl) -acetate A solution of 6.0 g. of 7,7-dimethyl-l-(cyanoacetylnorbornane in 50 ml. of dry methanol was saturated with hydrogen chloride gas and permitted to stand at room temperature for 15 hours. The mixture was concentrated to dryness under vacuum, and the residue was treated with ml. of benzene and 35 ml. of water. The mixture was refluxed for 2 hours; then the organic layer was separated, washed with water, and distilled to yield 3.6 g. of a colorless oil, B.P. 101105 C. (0.3 mm.).

Step 4.--Alpha-(7,7-dimethylnorbornane-1-carbonyl)- 3,5'-dicarbomethoxyacetanilide The reaction of 3.4 g. of methyl alpha-(7,7-dimethylnorbornane-l-carbonyl)acetate with 3.1 of 3,5 dicarbomethoxy aniline in 80 ml. of xylene containing 0.1 g. of sodium acetate was carried out in a manner similar to that described for coupler 18. The product obtained was recrystallized first from ethanol and then from acetonitrile to give 4.5 g. of a white solid with a M.P. of 156- 158 C.

Step 5.Alpha-(7,7-dimethylnorbornane 1 carbonyl)- alpha-(3-octadecylcarbamylphenylthio)-3',5' dicarbomethoxy-acetanilide The preparation of this compound from 4.0 g. of alpha- (7,7-dimethylnorbornane 1 carbonyl)-3',5'-dicarbomethoxyacetanilide and 4.05 g. of bis(3-octadecylcarbamyl phenyl)disulfide was carried out by a procedure similar to that used to prepare coupler 18. The product was recrystallized from carbon tetrachloride to give 5.1 g. of a white solid, M.P. 12913l C.

Step 6.Alpha-(7,7-dimethylnorbornane 1 carbonyl) alpha-(3-0ctadecy1carbamylphenylthio) 3',5 dicarboxyacetanilide A mixture of 4.1 g. of alpha-(7,7-dimethylnorbornane- 1-earbonyl) alpha (3 octadecylcarbamylphenylthio)- 3',5'-dicarbomethoxyacetanilide, 60 ml. of alcohol, and 8.4 ml. of 2N aqueous sodium hydroxide was heated at -50 C. for 45 minutes, then filtered. The filtrate was acidified with hydrochloric acid, and the material which Cil 14 separated was recrystallized from glacial acetic acid to give 2.5 g. of coupler 28, M.P. l26129 C.

Coupler 29.The reaction of equimolar quantities of methyl alpha-(7,7 dimethylnorbornane 1 carbonyl)- acetate (prepared as indicated for coupler 28 in steps 1, 2 and 3) and 5-['y-(2,4 di tert. amylphenoxy)butyramido]-2chloroaniline (prepared as indicated for coupler 10 in steps 1 and 2) was carried out by a procedure similar to that described in step 3 for coupler 4. The product was recrystallized several times from methanol to give coupler 29 as a white crystalline solid, M.P. 99101 C.

Coupler 30.-The reaction of 13.35 g. of 5-[ -(2,4-ditert.-amylphenoxy)-butyramido]-2-chloroaniline and 6.53 g. of methyl-l-methylcyclohexane 1 carbonylacetate in 100 ml. of xylene was carried out in a manner similar to that described for coupler 4 in step 3. The product was recrystallized several times from a mixture of hexane and ethyl acetate to give 10.5 g. of coupler 30, M.P. 113- 116 C.

Coupler 31 was prepared by the following steps:

Step 1.2,5-dichloro-4-(chlorosulfonyl)acetanilide To 3 liters of chlorosulfonic acid was added 300 g. of 3,5-dichlorosulfanilic acid sodium salt with stirring to a temperature between 45 and 50 C. The clear reaction mixture was stirred for one hour at room temperature. After the addition of sulfanilic acid had been completed, the mixture was heated on a steam bath overnight. The clear solution was then added dropwise to crushed ice and the white solid which separated was collected, dried, and recrystallized from benzene cyclohexane mixture, yielding g. of product, M.P. 149-151 C.

Step 2.-2,5-dichloro-4-[N'-(n-octadecyl)-N- methylsulfamyl] acetanilide To a solution of 440 g. of N-methyl-N-octadecylamine in 4 liters of dry pyridine at a temperature of 35 C. was added 470 g. of the product of step 1. The mixture was heated to 60 to bring about complete solution, then stirred at room temperature for one hour, after which time it was drowned in 40 liters of saturated brine. The solid which separated was collected and recrystallized from methanol, yielding 520 g. of product, M.P. 74- 76 C.

Step 3.-2,5-dichloro-4-[N'-(n-octadecyl)-N'-methylsulfamyl1aniline To a solution of 388 g. of the product of step 2 in 5 liters of absolute alcohol was added an aqueous solution of 100 g. of sodium hydroxide in 200 ml. of water. The resultant clear solution was refluxed for /2 hour, after which time it was cooled under tap water, whereupon a white solid separated. The mixture was diluted with an equal volume of cold distilled water and left at room temperature overnight. The solid was collected and recrystallized from 16 liters of methanol, yielding 253 g. of product, M.P. 84-85 C.

Step 4.Coupler 31 A solution of 250 g. of the product of step 3, 78 g. of methyl nt-pivalyl acetate, and 0.25 g. of anhydrous sodium acetate in 900 ml. of dry xylene was refluxed for 5 hours, during which time methanol distilled from the mixture. The clear reaction mixture was concentrated in vacuo and the residual glass was then recrystallized from methanol, yielding 14.3 g. of product, M.P. 6365 C.

Coupler 32 was prepared by the same reactions used to make Coupler 31 except that in step 1, an equivalent amount of Z-chlorosulfanilic acid sodium salt was used in place of 3,5-dichlorosulfanilic acid sodium salt. The recrystallized coupler had a M.P. of 75-75.5 C.

Coupler 33 was prepared by the same reactions used to make Coupler 31 except that in step 1 an equivalent amount of 2-chlorosulfanilic acid sodium salt was used in place of 3,5dichlorosulfanilic acid sodium salt and in step 2 an equivalent amount of N-phenyl-N-octadecylamine was used in place of N-methyl-N-octadecylamine. The recrystallized coupler had a M.P. of 9597.5 C.

Coupler 34 was prepared by the same reactions used to make Coupler 31 excepting that step 1 an equivalent amount of 2-chlorosulfanilic acid sodium salt was used in place of 3,5-dichlorosulfanilic acid sodium salt, and in step 2 an equivalent amount of N-benzyl-N-(l-methyldodecyl)amine was used in place of N-methyl-N-octadecylamine. The recrystallized Coupler 34 had a M.P. of 80-81 C.

Coupler 35 was prepared by the same reactions used to make Coupler 31 except that in step 2 an equivalent amount of N-phenyl-N-octadecylamine was used in place of N-methyl-N-octadecylamine. The recrystallized coupler had a M.P. of 7071 C.

Coupler 36 was prepared by the same reactions used to make Coupler 31 except that in step 2 an equivalent amount of N-benzyl-N-( l-methyldodecylJamine was used in place of N-methyl-N-octadecylamine.

Coupler 37 was prepared by the same reactions used to make Coupler 10 except that in step 3 an equivalent amount of ethyl u-(u,a-diphenylbutyryl)acetate was used in place of ethyl pivalylacetate. The recrystallized coupler obtained had a M.P. of 149l55 C.

Coupler 38 was prepared by the same reactions used to make Coupler 10 except that in step 3 an equivalent amount of ethyl a-(a-methyl-a-phenyl)propionyl acetate was substituted for ethyl ivalylacetate. The recrystallized coupler obtained had an M.P. of 9698 C.

Coupler 39 may be prepared according to a procedure similar to that described for Coupler 18 but from bis- (3-octadecylcarbamylphenyl)-disultide and a-(a-phenylisobutyryl)-4-chlorosulfonylacetanilide and subsequently forming the potassium salt monohydrate by refluxing a methanol solution of the crude product, filtering, concentrating the filtrate to one-half its original volume and treating with potassium acetate as described for Coupler 25. The a-(u-phenylisobutyryl)-4-chlorosulfonylacetanilide may be prepared by the reaction used to make Coupler 1 but using ethyl a-(a-phenylisobutyryl)acetate in place of ethyl pivalylacetate, and then treating the product with chlorosulfonic acid as described in the preparation of Coupler 24.

Coupler 40 may be prepared by reacting 3,5-dicarbomethoxyaniline with a-(u-phenylisobutyryl)acetate, followed by reaction with bis-(3-octadecylcarbamylphenyl)- disulfide, then subsequently hydrolyzing the product with aqueous sodium hydroxide, followed by acidification.

Coupler 41, a mixture of 40 g. of methyl a-pivalylacetate and 47 g. of diethylimino acetate in 200 ml. of xylene was refluxed for 1 hours, during which time methanol distilled from the mixture. The resultant solution was then concentrated in vacuo and the residual oil was distilled (B.P. l46-149 C. at 0.1 ml), yielding 59 g. of the coupler.

Coupler 42, a mixture of g. of 2-aminothiazol and 33 g. of methyl a-pivalylacetate in 200 ml. of xylene was refluxed for 2% hours, during which time methanol distilled from the mixture. The reaction mixture was left at room temperature for 3 days, after which time the solid which had separated was collected and recrystallized from a mixture of hexane and ethyl acetate, yielding 76 g. of product, M.P. 139-443 C.

Coupler 43 may be prepared by a method similar to that used for Coupler 20 excepting that dioctadecyl disulfide was used in place of bis-(3-tetradecylcarbamylphenyl disulfide.

Coupler 44 may be prepared by reacting Coupler 41 with bis-(3-octadecylcarbamylphenyl)-disulfide, followed by alkaline hydrolysis, and finally acidification.

Coupler 45 is prepared by the reactions used to prepare Coupler 42 but substituting 2-amino4,5-dicarbethoxythiazol for 2-aminothiazol.

Coupler 46, to a suspension of 64 g. of a-pivalyl-4- chlorosulfonyl acetanilide (prepared in Step 1 of the synthesis of Coupler 24) in 500 ml. of dry dioxane at 10 C. was added, with stirring, a solution of 12 g. of 1,6-hexanediamine and 61 g. of triethylamine over a period of one hour. The reaction mixture was stirred for an additional 30 minutes at 10 C., after which time the temperature of the mixture was raised to 25 C. over a two hour period. The mixture was heated, stirred at C. for two more hours, concentrated in vacuo to dryness, and the residue dissolved in 400 ml. of ethyl acetate. This solu tion was washed twice with 500 ml. portions of water, dried over magnesium sulfate, and concentrated to dryness. The residue was recrystallized twice from methyl alcohol, yielding the product, M.P. 98100 C.

Our couplers are especially adapted for incorporation in light sensitive emulsion of the developing-out type. They can be incorporated in photographic emulsions with any of the well-known coupler solvents, sometimes also known as porosity modifiers or high boiling crystalloidal materials or oil former of Mannes et al. U.S. Patent 2,304,939 and 2,304,340, and Jelley et al. U.S. Patent 2,322,027. Coupler solvent fl-(p-tert-butylphenoxy)ethyl alcohol of Jelley, 2,4-di-tert.-amylphenoxyethanol, and other mono-, di-, or trialkylphenoxy alcohols can be used to advantage with the couplers of our invention or with any coupler that is used or can be used with our emulsions.

Various surfactants can be used as dispersing agents in preparing coupler dispersions in gelatin for making photographic emulsions. The propylated naphthalenesulfonates such as Alkanol B. Antaron R275, Nekal BX-78 and Aerosol OS; the sodium alkyl benzenesulfonates such as Sul-fon-ate AA-lO, and Nacconol FSNO; sodium lauryl sulfate such as Tridupone 51-a; and the N (carbo-p-tert.-octylphenoxypentethoxy)glutarnate such as Triglutol-S may be used as dispersing agents for our couplers or for any coupler that is used in emulsions that are used in photographic products with our emulsions.

The emulsions can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added such as those described in Sheppard US. Patent 1,574,944, issued Mar. 2, 1926, Sheppard et al. U.S. Patent 1,623,499 issued Apr. 5, 1927, and Sheppard et al. U.S. Patent 2,410,689, issued Nov. 5, 1946.

The emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, Iridium, and platinum. Representative compounds are ammonium chloropalladate, potassium chloroplatinatc, and sodium chloropalladite, which are used for sensitizing n amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, issued Aug. 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith U.S. Patents 2,566,245, issued Aug. 28, 1951 and 2,566,263, issued Aug. 28, 1951.

The emulsions can also be chemically sensitized with gold salts as described in Waller et al. U.S. Patent 2,399,- 083, issued Apr. 23, 1946, and Damschroder et al. U.S. Patent 2,642,361, issued June 16, 1953. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2- aurosulfobenzothiazole methochloride.

The emulsions can also be chemically sensitized with reducing agents such as stannous salts (Carroll U.S. Patent 2,487,850, issued Nov. 15, 1949), polyamines, such as diethyl triamine (Lowe and Jones U.S. Patent 2,518,698, issued Aug. 15, 1950), polyamines, such as spermine (Lowe and Allen U.S. Patent 2,521,925, issued Sept. 12, 1959), or bis(p-aminoethyl)sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926, issued Sept. 12, 1950).

The emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Patents 1,846,301, issued Feb. 23, 1932; 1,846,302, issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White U.S. Patent 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Patents 2,112,140, issued Mar, 22, 1938', 2,165,338, issued July 11, 1939; 2,493,- 747, issued Jan. 10, 1950 and 2,739,964, issued Mar. 27, 1956; Brooker and Keyes U.S. Patent 2,493,748, issued Jan. 10, 1950; Sprague U.S. Patents 2,503,776, issued Apr. 11, 1950 and 2,519,001, issued Aug. 15, 1950; Heseltine and Brooker U.S. Patent 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Patent 2,734,900, issued Feb. 14, 1956; Van Lare U.S. Patent 2,739,149, issued Mar. 20, 1956; and Kodak Limited British patent 450,958, accepted July 15, 1936.

The emulsions can also be stabilized with the mercury compounds of Allen, Byers and Murray U.S. Patent 2,728,- 663, issued Dec. 27, 1955; Carroll and Murray U.S. Patent 2,728,664, issued Dec. 27, 1955; and Leubner and Murray U.S. Patent 2,728,665, issued Dec. 27, 1955; or with gold salts as described in Damschroder U.S. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers U.S. Patent 2,597,915, issued May 27, 1952; the triazoles of Heimbach and Kelly U.S. Patent 2,444,608, issued July 6, 1943; the azaindenes of Heimbach and Kelly U.S. Patents 2,444,605 and 2,444,606, issued July 6, 1948; Heimbach U.S. Patents 2,444,607, issued July 6, 1948 and 2,450,397, issued Sept. 28, 1948; Heimbach and Clark U.S. Patent 2,444,609, issued July 6, 1948; Allen and Reynolds U.S. Patents 2,713,541, issued July 19, 1955 and 2,743,181, issued Apr. 24, 1956; Carroll and Beach U.S. Patent 2,716,062, issued Aug. 23, 1955; Allen and Beilfuss U.S. Patent 2,735,769, issued Feb. 21, 1956; Reynolds and Sagal U.S. Patent 2,756,147, issued July 24, 1956; Allen and Sagura U.S. Patent 2,772,164, issued Nov. 27, 1956; and those disclosed by Birr in Z. wiss. Phot., vol. 47, 1952, p. 2-28; the disulfides of Kodak Belgian Patent 569,317, issued July 31, 1958; the quaternary benzothiazolium compounds of Brooker and Staud U.S. Patent 2,131,038, issued Sept. 27, 1938 or the polymethylene bisbenzothiazolium salts of Allen and Wilson U.S. Patent 2,694,716, issued Nov. 16, 1954 (e.g., decamethylene-bisbenzothiazolium perchlorate); or the zinc and cadmium salts of Jones U.S. Patent 2,839,405, issued June 17, 1958; and the carboxymethylmercapto compounds of Murray, Reynolds and VanAllan U.S. Patent 2,819,965, issued Jan. 14, 1958.

The emulsions may also contain speed increasing compounds of the quaternary ammonium type of Carroll U.S. Patent 2,271,623, issued Feb. 3, 1942; Carroll and Allen U.S. Patent 2,288,226, issued June 30, 1942; and Carroll and Spence U.S. Patent 2,334,864, issued Nov. 23, 1943; or the quaternary ammonium salts and polyethylene glycols of Piper U.S. Patent 2,886,437, issued May 12, 1959; and the polyethylene glycol type of Carroll and Beach U.S. Patent 2,708,162, issued May 10, 1955; or the thiopolymers of Graham and Sagal U.S. application Ser. No. 779,839, filed Dec. 12, 1958, now U.S. Patent 3,046,- 129, or Dann and Chechak U.S. application Ser. No. 779,874, filed Dec. 12, 1958, now U.S. patent 3,046,134.

The emulsions may contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5- pentane diol as described in Milton and Murray U.S. application Ser. No. 588,951, filed June 4, 1956, now U.S. Patent 2,960,404, issued Nov. 15, 1960; an ester of an ethylene bis-glycolic acid such as ethylene bis(methyl glycolate) as described in Milton U.S. application Ser. No. 662,564, filed May 31, 1957, now U.S. Patent 2,904,- 434, issued Sept. 15, 1959; bis(ethoxy diethylene glycol) succinate as described in Gray U.S. application Ser. No. 604,333, filed Aug. 16, 1956, now U.S. Patent 2,940,854, issued June 14, 1960; or a polymeric hydrosol as results from the emulsion polymerization of a mixture of an amide of an acid of the acrylic acid series, an acrylic acid ester and a styrene-type compound as described in Tong U.S. Patent 2,852,386, issued Sept. 16, 1958. The plasticizer may be added to the emulsion before or after the addition of a sensitizing dye, if used.

The emulsions may be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo-(2,2,2)-octene-2,3,5, 6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll U.S. Patents 2,725,294 and 2,725,295, both issued Nov. 29, 1955; a cyclic 1,2-diketone such as cyclopentane-1,2-dione as described in Allen and Byers U.S. Patent 2,725,305, issued Nov. 29, 1955; a bisester of methanesulfonic acid such as l,2-di(methanesulfonoxy) ethane as described in Allen and Laakso U.S. Patent 2,726,162, issued Dec. 6, 1955; 1,3-dihydroxyrnethylbenzimidazol-Z-one as described in July, Knott and Pollak U.S. Patent 2,732,316, issued Jan. 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as it-methyl gluataraldehyde bis-sodium bisulfite as described in Allen and Burness, U.S. patent application Ser. No. 556,031, filed Dec. 29, 1955, abandoned Apr. 21, 1960; a bis-aziridine carboxamide such as trimethylene bis(1-aziridine carboxamide) as described in Allen and Webster U.S. patent application Ser. No. 599,891, filed July 25, 1956, now U.S. Patent 2,950,197, issued Aug. 23, 1960; or 1,3-di-hydroxy dioxane as described in Jeffreys U.S. Patent 2,870,013, issued Jan. 20, 1959; or bisisocyan-ate as described in Henn et a1. U.S. patent application Ser. No. 805,357, filed Apr. 10, 1959, now U.S. Patent 3,103,437.

The emulsions may contain a coating aid such as sapomin; a lauryl or oleyl monoether of polyethylene glycol as described in Knox and Davis U.S. Patent 2,831,766, issued Apr. 22, 1958; a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis U.S. Patent 2,719,087, issued Sept. 27, 1955; an acylated alkyl taurine such as the sodium salt of N-oleyl-N-methyl taurine as described in Knox, Twardokus and Davis U.S. Patent 2,739,891, issued Mar. 27, 1956; the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg and Wilson U.S. Patent 2,843,- 487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a water-soluble maleopimarate and a substituted glutamate salt as described in Knox and Fowler U.S. Patent 2,823,123, issued Feb. 11, 1958; an alkali metal salt of a substituted amino acid such as disodium N-(carbo-p-tert-octylphenoxypentaethoxy) glutamate as described in Knox and Wilson U.S. patent application Ser. No. 600,679, filed July 30, 1956, now U.S. Patent 3,038,804; or a sulfosuccinamate such as tetrasodium N (1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate or N- lauryl clisodium sulfosuccinamate as described in Knox and Stenberg U.S. patent application Ser. No. 691,125, filed Oct. 21, 1957, now U.S. Patent 2,992,108, issued July 11, 1961; or a sodium salt of an alkylarylpolyether sulfonate of U.S. patent application Ser. No. 753,642, filed Aug. 7, 1958, now U.S. Patent 3,026,202, issued Mar. 20, 1962.

The couplers which we have described may be used in various kinds of photographic emulsions. They may be added to the emulsion before or after any sensitizing dyes which are used. Various silver salts may be used as the sensitive salt, such as, silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver bromoiodide. The couplers are used in emulsions intended for color photography, for example, emulsions containing color-forming couplers of emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed packet type, such as described in Godowsky US. Patent 2,698,794, issued Ian. 4, 1955; or emulsions of the mixedgrain type, such as described in Carroll and Hanson US. Patent 2,592,243, issued Apr. 8, 1952. The couplers can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly inside the silver halide crystal, such as those described in Davey and Knott US. Patent 2,592,250, issued Apr. 8, 1952.

The couplers may also be used in emulsions intended for use in diffusion transfer processes which utilize the undeveloped silver halide in the nonimage areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer. Such processes are described in Rott US. Patent 2,352,014, issued June 20, 1944, and Land US. Patents 2,584,029, issued Jan. 29, 1952; 2,698,236, issued Dec. 28, 1954 and 2,543,181, issued Feb. 27, 1951; and Yackel et al. US. patent application Ser. No. 586,705, filed May 23, 1956, now US. Patent 3,020,155, issued Feb. 6, 1962. They may also be used in color transfer processes which utilize the diffusion transfer of an imagewise distribution of developer, coupler or dye, from a lightsensitive layer to a second layer, while the two layers are in close proximity to one another. Color processes of this type are described in Land US. Patents 2,559,643, issued July 10, 1951 and 2,698,798, issued Jan. 4, 1955; Land and Rogers Belgian Patents 554,933 and 554,934, granted Aug. 12, 1957; International Polaroid Belgian Patents 554,212, granted July 16, 1957 and 554,935, granted Aug. 12, 1957', Yutzy US. Patent 2,756,142, granted July 24, 1956 and Whitmore and Mader US. patent application Ser. No. 734,141, filed May 9, 1958, now abandoned. They may also be used in emulsions intended for use in a monobath process such as described in Haist et al. US. Patent 2,875,048, issued Feb. 24, 1959, and in web-type processes, such as the one described in Tregillus et al. US. patent application Ser. No. 835,473, filed Aug. 24, 1959, now US. Patent 3,179,517.

In the preparation of the silver halide dispersions employed for preparing silver halide emulsions, there may be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound. Some colloids which may be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in US. Patent 2,327,808 of Lowe and Clark, issued Aug. 24, 1943; a water-soluble ethanolamine cellulose acetate as described in Yutzy US. Patent 2,322,085, issued June 15, 1943; a polyacrylamide or an imidized polyacrylamide as described in Lowe, Minsk and Kenyon US. Patent 2,541,- 474, issued Feb. 13, 1951; zein as described in Lowe U.S. Patent 2,563,791, issued Aug. 7, 1951; a vinyl alcohol polymer containing urethane carboxylic acid groups of the type described in Unrnh and Smith US. Patent 2,768,- 154, issued Oct. 23, 1956', or containing cyano-acetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest, US. Patent 2,808,331, issued Oct. 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described in US. Patent 2,852,382, of lllingsworth, Dann and Gates, issued Sept. 16, 1958.

1f desired, compatible mixtures of two or more of these colloids may be employed for dispersing the silver halide in its preparation. Combinations of these antifoggants, sensitizers, hardeners, etc., may be used.

Photographic emulsions containing our couplers are color developed by developer solutions containing any of the well known primary aromatic amino silver halide developing agents such as the phenylene diamines including the alkylphenylenediamines and the alkyltoluenediamines. These are generally used in the salt form such as the hydrochloride or sulfate. The p-aminophenols and their substitution products may also be used where the amino group is substituted. All of the developing agents have an unsubstituted amino group which enables the oxidation product of the developer to couple with the color forming coupler compounds to form a dye image.

Typical developers containing these developing agents are as follows:

Developer 1 2-amino-5-diethylaminotoluene hydrochloride grams 2.5 Sodium sulfite (anhydrous) do 5.0 Sodium carbonate (anhydrous) do 20.0 Potassium bromide do 2.0 Water to liter 1.0

Developer 2 N ethyl ,3 methanesulfonamidoethyl 3 methyl- 4-aminoaniline sulfate grams 2.0 Sodium sulfite (anhydrous) do 0.6 Sodium carbonate (anhydrous) do 30.0 Water to liter 1.0

The couplers of our invention such as couplers 18, 20, 25 and 28 are capable of reacting with oxidized color developer to form a diffusible dye and are therefore useful in the color diffusion transfer processes such as disclosed in Whitmore et a1. Ser. No. 734,141, May 9, 1958, now abandoned, Williams et a1. Ser. No. 780,710, Dec. 16, 8, now abandoned. Accordingly, the emulsions having these couplers in contiguity can be exposed and developed to form a dilfusible dye image in the region of development which dye image transfers by diffusion to a reception layer.

Our invention is further illustrated by the following specific examples showing how our couplers are incorporated in photographic emulsions and then used to produce yellow dye images having valuable light absorption characteristics for color photography.

EXAMPLE I 25 ml. of a dispersion of 1 g. of coupler 10 and 0.5 g. of di-n-butylphthalate coupler solvent in 2.2 g. of gelatin was mixed with 5 ml. of a conventional-medium speed silver bromoiodide emulsion and the mixture was coated on a suitably-subbed cellulose acetate support. After being dried, the coating was exposed under an image and developed in Developer 2 to form a negative silver and yellow dye image. The silver image and the residual silver halide were removed by treatment with a conventional ferricyanide bleach followed by a hypo fixing bath leaving a yellow negative image having a xmax (i.e. maximum absorption) at a wavelength of 444 m and exhibiting particularly good absorption characteristics.

EXAMPLE II Another film sample coated with the above emulsion was exposed and given the same processing, but with Developer l. The yellow dye image produced also had very desirable absorption characteristics and a Amax value of 448 mp" EXAMPLE III An emulsion coating was made as in Example 1 but in which 1 g. of coupler 2 and 2 g. of di-n-butylphthalate was incorporated instead of coupler 10. This was exposed and developed with Developer 1. The dye image produced had a maximum absorption at 444 my. and the absorption characteristics shown as Curve D of FIGURE 2 of the accompanying drawing.

21 EXAMPLE 1v An emulsion coating was made as in Example I but using 1 g. of coupler 9 and 0.25 g. of di-n-butylphthalate in place of coupler 10. This was exposed and developed in Developer 2. After removal of the silver and residual silver halide by conventional bleaching and fixing, a yellow dye image having a Arnax value of 444 m was produced.

EXAMPLE V An emulsion coating was made as in Example I but using coupler 6 in place of coupler 10. This was exposed and processed as in Example I to produce a good yellow dye image having a )tmax value of 438 mu.

EXAMPLE VI Another film sample coated with the emulsion of Example V was given the same processing but with Developer 1. This produced a good yellow dye image having a Amax value of 442 m EXAMPLE VII Similarly, other couplers of our invention were incorporated in emulsion layers, exposed to an image and developed to produce yellow dye images having valuable characteristics for use in color photography.

The following table lists Amax values for the dyes produced from representative couplers of our invention.

TABLE C Max. value in m of dye produced in silver halide emul ion layer containing coupler by color Ratio of eouplcr development withto di-nbutylphthalato Developer 1 Developer 2 1:2 432 436 1:2 444 1:2 440 1:% 448 444 1:2 448 442 1;% 442 438 1:% 444 440 1:2 438 1:% 446 444 1:}6 448 444 1:% 458 454 1:94 455 448 1 2 448 1:2 446 19/6 444 442 1:2 448 448 1:% 444 444 1: M 455 454 1:%; 462 458 1: 95 456 452 195 458 454 11% 457 453 11% 462 459 1:% 464 458 lzl 458 453 l 452 450 Table D lists )tmax values for dyes produced by the color development of exposed photographic elments containing mordanted couplers of the type used for image transfer processes. These dyes were produced by development with a developer solution of the type of Developer 2 but in which 4-N-ethyl-N-fi-hydroxyethylamino aniline was used as the developing agent in place of N-ethyl-A- EXAMPLE VIII A sample of the emulsion coating of Example I was compared with a similar coating in which the a-benzoy] analogue of our coupler 4 was used. These film samples were compared for printout, by exposing for 30 hours in a Xenon Arc Fadeometer. The film sample containing our coupler at the end of the test showed only a 0.5% reduction in transmission as compared to the 4.5% reduction shown by the film sample containing the a-benzoyl analogue of our coupler. The film samples were compared for yellowing by storing for one week at 140 F. and RH. The film sample containing our coupler showed no reduction in transmission as compared to a 1% reduction in transmission produced by this treatment in the other film sample.

The valuable light absorbing properties illustrated in the examples above which characterize the dyes produced by color development of our novel couplers is further illustrated by the spectrophotometric curves shown by the accompanying drawings, FIGURES 1, 2, 3, 4 and 5.

FIGURES l, 2 and 3 of the drawings show the spectrophotometric curves for the dyes produced by color development of coupler 11 in the emulsion of Example 4, coupler 2 in the emulsion of Example 3, and coupler 10 in the emulsion as described in Example 2, respectively. These figures demonstrate the high absorption our dyes have for blue light and the low and uniform absorption they have for green and red light which makes them very desirable for use in color photography.

Our dyes are not only characterized by having very deirable light absorption properties when they are originally formed but they retain these properties to an unexpected degree after being exposed to heat and light over a period of time.

Table E below illustrates the stability of dyes from representative couplers of our invention when they were exposed in a Xenon Arc Fadeometer.

TABLE E Dyes produced by color development of an exposed silver halide emulsion layer containing:

Decrease in dye dcnity at )trnax.

Irodured by 30 hours exposure in Fndeoiueter.

FIGURE 1 of the drawings further illustrates the good stability of our dyes to exposure to light. Spectrophotometric curves A, B and C represent the light absorption characteristics of our dye before exposure, after 30 hours exposure, and after 50 hours exposure in the Fadeometer, respectively showing that only a relatively small amount of dye fading was produced by this severe test. The basic shape of the curve is unchanged even after 50 hours of exposure.

FIGURE 3 of the drawings still further illustrates the characteristic stability of dyes from our couplers. Curves F and G were obtained for an emulsion containing the dye from our coupler l0, a-pivalyI-S-[' '-(2,4-di-tert-amylphcnoxy) butyramido]-2 chloroacetanilide as formed and after 30 hours exposure in the Xenon Arc Fadeometer. This treatment caused the dye to fade only 0.12 density unit.

The excellent stability of the dyes from our couplers is unexpected in view of the relatively poor stability of dyes from coupler analogues of our couplers. The importance of the tertiary carbon connected to the carbonyl grou of our couplers is illustrated by a comparison of FIGURE 3 with FIGURE 4 and with FIGURE 5.

Spectrophotometric curves H and I of FIGURE 4 show the light absorption characteristics of the dye produced in an emulsion made as described in Example 1 but which contained the coupler a-(a'-methylbutyryl) 5 ['y"-(Z,4- di tert amylphenoxy)-butyramido]-2-chloroacetanilide. This coupler is an isomer of coupler 10 (used to make the group attached to the carbonyl group in place of a (CH C group.

FIGURE 4 shows that 30 hours of exposure to the Xenon Arc Fadeometer reduced the dye density by 0.70 unit. The corresponding loss in density from our coupler shown in FIGURE 3 was only 0.11 density unit.

Spectrophotometric curves J and K of FIGURE 5 show the light absorption characteristics of the dye produced in an emulsion made as described in Example 1, but which contained the coupler u-(flB'-dimethy1butyryl)- 5-[a" (2,4-di-tert-amylphenoxy)acetamido] 2 chloroacetanilide in place of coupler 10. This coupler difiers primarily from coupler 10 in that it has a CI-I group separating the tertiary butyl group from the carbonyl group of the coupler. The comparison between curves J and K show that 30 hours exposure in the Fadeometer roduced a loss in dye density of 0.45 density unit.

We claim:

1. A compound selected from those having the formulas:

o R J-ii-CHlis/ and th nks- 3 wherein J represents a member selected from the class consisting of a l-alkyl-cyclohexyl radical in which the alkyl radical has from 1 to 18 carbon atoms, a l-alkoxyl-cyclohexyl radical in which the alkyl radical has from 1 to 18 carbon atoms, a l-alkoxyalkyl-l-cyclohexyl radical in which the alkoxyalkyl radical has from 2 to 18 carbons atoms, l-phenyl-l-cyclohexyl, l-toIyl-l-cyclohexyl, 7,7-dimethylnorbornyl, a 2-alkyl 7,7 dimethylnorbornyl radical in which the alkyl group has from 1 to 18 carbons, 2-phenyl-7,7-dimethylnorbornyl and 2-tolyl-7,7-dimethylnorbornyl such that a tertiary carbon atom in the said I group is attached directly to the carbonyl group of the coupler moiety and such that the I group taken together with the carbonyl group has from to 32 carbon atoms; A and A each represents a member selected from the class consisting of the hydrogen atom, the chlorine atom, the bromine atom and an -SB radical; B represents a member selected from the class consisting of 1,3,4-oxadiazolyl, benzoxazoyl, phenyltetrazolyl, a 3-alkylcarbamylphenyl in which the alkyl group has from 1 to 18 carbon atoms, a 3-alkyl-4-methoxyphenyl in which the alkyl group has from 1 to 18 carbon atoms, a dialkyl-4-aminophenyl radical in which the alkyl groups have from 1 to 18 carbon atoms, and octadecyl; R and R each represent a member selected from the class consisting of phenyl, 2- chlorophenyl, 4-sulfophenyl, Z-dimethylaminophenyl, a 2-halo-5-alkamidophenyl radical, a Z-methoXyS-allcamidophenyl radical, a 4-alkamidophenyl radical, a 4-mothoxyphenyl radical, a 4-sulfamylphenyl radical, a 2-chloro sulfonamidophenyl radical, 3,5 dicarboxyphenyl, alkyl esters of 3,5-clicarboxyphenyl in which the alkyl moiety has from 1 to 18 carbon atoms, a Z-phenoxy-S- carbamylphenyl radical, 3,5-dicarbamylphenyl, hydrogen, an alkyl group of from 1 to 18 carbon atoms, thienyl, 5- carbethoxythienyl, S-carbethoxyfuryl, thiazoyl, 4-methylthiazolyl, 4-phenylthiazolyl, 4-fury1thiazolyl, 4-methy1-5- carboxymethylthiazolyl, 4,5-diphenylthiazolyl, 4-carboxymethylthiazolyl, 4mor p-acylaminophenylthiazolyl, 4,5- dicarbethoxythiazolyl, 4-methyl 5 carboxymethylthiazolyl, 4-methyl 5 carbethoxythiazolyl, 5-carboxythiazolyl, 5 carbomethoxythiazolyl, S carbethoxythiazolyl, benzthiazolyl, oxazolyl, imidazolyl, benzimidazolyl, pyridyl, S-acylaminopyridyl, quinolyl, 2,6-dihydroxy 4-methylpyrimidyl, 5-carbomethoxyethyl 1,3,4 thiadiazolyl, 1, 3,4-oxodiazolyl, a 1,2,4-triazolyl radical and 1,3,5-triazinyl; D and D each represent a member selected from the class consisting of the group, the

group, the NI-ISO,- group and the SO NH- group; and W represents a bivalent group selected from the class consisting of a phenylene group and an alkylene group.

2. The yellow dye-forming coupler u-pivalyl-5-[-/-(2,4- di-tert-amylphenoxy) -butyramido -2-chloroacetanilide.

3. The yellow dye-forming coupler a-pivalyl-5-[a'-(2,4- di-tert-amylphenoxy) acetamido -2-chloroacetanilide.

4. The yellow dye-forming coupler a-(l-methylcyclohexane-l-carbonyl) 5 ['y-(2,4-di-tert-amylphenoxy)- butyramido] -2-chloroacetanilide.

5. The yellow dye-forming coupler a-(a-methoxyisobutyryl) 5 [it"-(2,4-di-tert-amylphenoxy)acetamido]- Z-chloroacetanilide.

6. The yellow dye-forming coupler -(7,7-dimethylnorbornane-l-carbonyl) 5 ['y-(2,4-di-tert-amylphenoxy) butyramido-2-chloroacetanilide.

7. The yellow dye-forming coupler a-pivalyl-a-(3-octadecylcarbamylphenylthio)-4 sulfoacetanilide potassium salt.

8. A compound selected from those having the formulas:

I 0 O R J lE-CHEN and Jil- ICH-PJ-IL-Q wherein J represents a member selected from the class consisting of a I-alkyI-cyclohexyl radical in which the alkyl radical has from 1 to 18 carbon atoms, a I-alkoxy- I-cyclohexyl radical in which the alkyl radical has from 1 to 18 carbon atoms, a I-alkoxyalkyl-l-cyclohexyl radical in which the alkoxyalkyl radical has from 2 to 18 carbons atoms, I-phenyl-I-cyclohexyl, I-tolyI-I-cyclohexyl, 7,7-dimethylnorbornyl, a 2-alkyl-7,7-dimethylnorbornyl radical in which the alkyl group has from I to 18 carbons, Z-phenyl-7,7-dimethylnorbornyl and 2-tolyl-7,7-dimethylnorbornyl such that a tertiary carbon atom in the said J group is attached directly to the carbonyl group of the coupler moiety and such that the I group taken together with the carbonyl group has from to 32 carbon atoms; A and A each represents a member selected from the class consisting of the hydrogen atom, the chlorine atom, the bromine atom and an SB radical; B represents a member selected from the class consisting of 1,3,4-oxadiazolyl, benzoxazoyl, phenyltetrazolyl, a 3-alkylcarbamylphenyl in which the alkyl group has from 1 to 18 carbon atoms, a 3-alkyl-4-methoxyphenyl in which the alkyl group has from 1 to 18 carbon atoms, a dialkyl-4-amin0- phenyl radical in which the alkyl groups have from 1 to 18 carbon atoms, and octadecyl; R and R each represent a member selected from the class consisting of phenyl, 2- chlorophenyl, 4-sulfophenyl, Z-dimethylaminophenyl, a 2-halo-5-alkamidophenyl radical, a Z-methaxy-S-alkamidopenyl radical, a 4-alkamidophenyl radical, a 4-methoxyphenyl radical, a 4-sulfamylphenyl radical, a 2-chloro- 5-sulfonamidophenyl radical, 3,5-dicarboxyphenyl, alkyl esters of 3,5-dicarboxyphenyl in which the alkyl moiety has from 1 to 18 carbon atoms, a Z-phenoxy-S-carbamylphenyl radical, 3,5-dicarbamylphenyl, hydrogen, an alkyl group of from 1 to 18 carbon atoms, thienyl, 5-carbethoxythienyl, 5-carbethoxyfuryl, thiazolyl, 4-methylthiaz0lyl, 4-phenylthiazolyl, 4-furylthiazolyl, 4-methyl 5 carboxymethylthiazolyl, 4,5 diphenylthiazolyl, 4 carboxymethylthiazolyl, 4-mor p-acylaminophenylthiazolyl, 4,5- dicarbethoxythiazolyl, i -methyl 5 carboxymethylthiazolyl, 4-methyl 5 carbethoxythia zolyl, S-carboxythiw zolyl, 5 carbomethoxythiazolyl, 5 carbethoxythiazolyl, benzthiazolyl, oxazolyl, imidazolyl, benzimidazolyl, pyridyl, S-acylaminopyridyl, quinolyl, 2,6-dihydroxy-4-methylpyrimidyl, 5-carbomethoxyethyl-l,3,4-thiadiazolyl, 1, 3,4-oxodiazolyl, a 1,2,4-triazolyl radical and 1,3,5-triazinyl, except that R in formula I is defined as phenyl, 2- chlorophenyl, 4-sulfophenyl, Z-dimethylaminophenyl, a 2-halo-5-alkamidophenyl radical, a Z-methoxy-S-alkamidophenyl radical, a 4-alkamidophenyl radical, a 4-methoxyphenyl radical, a 4-sulfamylphenyl radical, a 2-chloro 5 sulfonamidophenyl radical, 3-5-dicarboxyphenyl, alkyl esters of 3,5-dicarboxyphenyl in which the alkyl moiety has from I to 18 carbon atoms, a Z-phenoxy-S- carbamylphenyl radical or 3,5-dicarbamylphenyl; D and D each represent a member selected from the class consisting of the group, the

group, the NHSO group and the SOgNH- group,-

and W represents a bivalent group selected from the class F wherein J represents a member selected from the class consisting of l-alkyl-cyclohexyl radical in which the alkyl radical has from 1 to I 8 carbon atoms, a l-alkoxy-I-cyclohexyl radical in which the alkyl radical has from I to 18 carbon atoms, a I-alkoxyalkyl-lcyclohexyl radical in which the alkoxyalkyl radical has from 2 to 18 carbon atoms, l-phenyl-Lcyclohexyl, I-tolyl-I-cyclohexyl, 7,7- dimethylnorbornyl, a 2-alkyl-7,7-dimethylnorbornyl radical in which the alkyl group has from 1 to 18 carbons, 2-phenyl-7,7-dimethylnorbornyl and 2-tolyl7,7-dimethylnorbornyl such that a tertiary carbon atom in the said I group is attached directly to the carbonyl group of the coupler moiety and such that the I group taken together with the carbonyl group has from 5 to 32 carbon atoms; A represents a member selected from the class consisting of the hydrogen atom, the chlorine atom, the bromine atom and an SB radical in which B represents a member selected from the class consisting of 1,3,4-oxadiazolyl, benzoxazoyl, phenyltetrazolyl, a 3-alkylcarbamylphenyl in which the alkyl group has from 1 to 18 carbon atoms, a 3-alkyl-4-methoxyphenyl in which the alkyl group has from I to 18 carbon atoms, and a diaIkyl4-aminophenyl radical in which the alkyl groups have from 1 to 18 carbon atoms and octadecyl; R is a member selected from the class consisting of a phenyl, 2-chlorophenyl, 2-dimethylaminophenyl, a 2-halo-5-alkamidophenyl radical, a 2-methoxy-S-alkamidophenyl radical, a 4-alkamidophenyl radical, a 4-methoxyphenyl radical, a 4sulfamylphenyl radical, a 2-chloro-5-sulfonamidophenyI radical, 3,5-dicarboxyphenyl, alky esters of 3,5 dicarboxypheny in which the alkyl moiety has from I to 18 carbon atoms, a 2-phenoxy-5-carbamylphenyl radical, and 3,5-dicarbamylphenyl radical.

References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

UNITED STATES PATENTS 2,950,314 8/1960 De Cat et a1 260507 R OTHER REFERENCES Wahlberg, Chemical Abstracts 15, 1490-1492 (1921).

DANIEL D. HORWITZ, Primary Examiner US. Cl. X.R.

96-55, 56.2, 56.3, 56.4, 56.5, 56.6, 100; 260-247.7 R, 249.5, 256.4 R, 256.5 R, 287 R, 204.8 R, 295 R, 305, 306.8 R, 307 R, 308 R, 309, 309.2 R, 347.2, 347.3, 397.7, 319, 556 R, 557 R, 558 R, 559 R, 561 R, 562 R 

